Temperature compensated conductivity cell electrode



E. R. BEHN May 2, 1950 TEMPERATURE COIPENSATED CONDUCTIVITY. CELL ELECTRODE Filed April 23, 1949 2 Sheets-Sheet 1 rl t I I I I l l l I I l l I l I l i I I I I I i I l I I I l l I I I I l l IIL Y INVENToR. EUCH. 301m IMM TJ'R/VY May 2, 1950 E. R. Br-:HN 2,505,936

TEMPERATURE COMPENSATED CONDUCTIVITY CELL ELECTRODE Filed April 23. 1949 2 Sheets-Sheet 2 I" .4 lo'ooo w 9 B. 7 e s .4 s

RES/S TA NCF INVENTOR. Eljo R Bela! 'Ew/KM which ouate measuring system,

''esistances used in Patented May 2, 1950 TEMPERATURE C DUCTIVITY CE Eric R. Behn,

trol Instrument Com MPENSAIED CON- LL ELECTRODE Garden. City, N. Y.,

pany, Inc.,

assignor to Con- Brooklyn, N. Y.,

a corporation o! New York Application April 23, 1949, Serial No. 89,332 2 Claims. (Cl. 1175-183) This invention relates to improvements in electrical measuring systems and has particular reference to a system for directly indicating the conductivity of a solution.

In systems of the above category it is necessary to compensate for temperature variation of the solution under test, in order to obtain an indication reading directly in terms of electrolyte concentration. In the past this has been accomplished by a manually settable compensator may be set according to the indications of a thermometer, or by various forms of temperature compensating resistors all of which have a common fault which will hereinafter be discussed, and which are avoided by this invention.

In an electrolytic solution of a given concentration such as, for instance, fresh water contaminated with sea water, thereexists a definite relationship of temperature to resistance. However, this relationship does not lend itself to a simple analytic expression for the reason that the relationship, as determined, becomes a function of the determining or measuring means.

The problem, therefore, resolves itself into one fof producing la. compensated measuring system whose variation negligible.

An object of this invention is to produce an of indication with temperature is 'element having a co-eillcient o1' resistance with temperature which, when combined with an adewill have the desired variation in resistance with temperature.

ductivlty cell to produce the required variation in resistance with temperature.

The invention is illustrated, by way of example, in its adaptation to a metering system such as is disclosed in the patent to Ellis, #2,306,691, issued December 29, .1942, and reference is made thereto for a complete understanding of the operation of the circuit.

y Briefly, and as shown herein, the vmeter includes ilxed coils 6 and 1 energized by connection tothe input 'terminals 8 and 9 for a source of alternating current. Pivotally mounted in the field of said coil are the rigidly connected movable coils i0, Il and l2, the first two of which are physically parallel while the last mentioned is at K right angles to the other two. Coil i2 carries an Ihe inventive idea herein involved is capable o f receiving a variety of expressions one of which for the purpose of illustration is shown inthe accompanying drawings and describedv in the following specification; y derstood, however, vthat the drawings and the speciilcation are employed merely to facilitate the description of 'the invention as a whole and not to define the limits thereof, reference being made to the appended claims for that purpose. In the drawings: Fig. 1 is a diagrammatic view of a salinity metering system showing the application of the present invention thereto;

Fig. 2 is an enlarged vertical section through a conductivity cell illustrating its construction in accordance with the invention herein described; Fig. 3 is a section on the line 3 3 o! Fig. 2; Fig. 4 is a graphic view showing the variation in resistance with temperature of the conductivity cell, ando! its compensating element; and

Fig. 5 is 4a schematic diagram of afnetworlr` of connection with the conit is to be expressly un-l indicator i3 which indicator moves over a calibrated scale il to indicate saline concentration in parts per million or any other chosen units.

The coils It, Ii and l2 are all connected in series and, by way of various resistors, with the secondary i6 of transformer i5. As applied in this invention, one circuit is established by way of resistor i1 whose function it is to limit-the current in the coils, coil I 0 and coil i2 in series, and the resistance of the saline liquid under test; and the second circuit is established by way of resistor il, coils i0, i 2 and ii in series and a resistance network including the temperature conipensating element hereinafter to be described.

Referring to Fig. 1, two conductivity cells il and I9 are shown which, by way of the switches 20 and 2i, may alternatively be connected to the metering circuit. The cells may be located at different points through which the liquid under test will circulate, and may be cyclically or manually connected to the metering circuit for the purpose of test.

The salinity cell which comprises this invention is illustrated in Fig. 2 wherein it is shown to be formed of a heat conducting casing 22 filled with an insulating material 23 through which pass a pair of electrodes 2l and 25. Electrode 24 is solid and is composed of or plated with a metal which is non-reactive to the liquid under test. Electrode 25 is hollow but otherwise similar 'in' shape and material to electrode 24. Y

Within the confines of electrode 25 is placed a semi-conductor 26, such as is commercially available under the name of 'I'hermistor, one end 21 of which is electrically connected at 2l to the bottom plug 3| of electrode 25. The other end 29 of the semi-conductor is extended upwardly, by means of the insulated lead 30, through the top of the electrode in order that electrical connection 3 ma;1 be madethereto. In order to insulate the semi-conductor from the metallic shell within which it is contained, a dielectric 32 fills the space surrounding it, ailording it both mechanical support and electrical insulation. However, 'it is essential that the variation in current in the Thermistor when connected in the circuit does not cause any temperature gradient or Variation in temperature gradient between the Thermistor l and the liquid` under test due to its own power diS- sipation, and also that the temperature of the liquid under test be communicated to the 'I'hermistor in order that its variation in resistance with temperature be available as a controlling element. Resistor I1 limits the currentin the circuit to a safe value, and the insulating material 32 must have excellent properties of heat conductivity as well asgood dielectric properties.

1n order to acquire material with the required characteristic, various experiments were conducted, using liquids and Vsolid materials and mixtures thereof, such as thermo-setting varnishes, glycerin, transformer oil, rosin oil, mixtures of rosin oil and finely comminuted silica, and mixtures of silicone iluid of low viscosity and iinely comminuted silica. The last named mixture, consisting of a semi-solid, proved to be the most efflcient, having the required heat conductivity characteristic, the required dielectric property, and the required mechanical and chemical inactivity which` would coact with the Thermistor without injury thereto. This material is injected into the space around the Thermistor within the electrode 25 by removing the plug 3l; and after filling the space surrounding the Thermistor and replacing said plug, the electrode is then vacuum impregnated with silicone iiuid to make certain that no voids remain. Thus the silicone-silica mixture 32 surrounds the Thermistor, coupling it mechanically and thermally to the wall of the electrode 25, and the excess silicone fluid, due to the vacuum impregnation and to any thermal expansion, iills the capillary bore 33 directly above.

Unlike any other temperature compensating re"- sistor, the unit is not sealed and yet it is contained substantially within and in intimate contact with the liquid whose temperature initiates its response. There isv no change in characteristic due tothe build-up of pressure due to thermal expansion; nor any danger of contamination, although the element is not sealed, because of the iineness of the capillary bore 33. There is also no leakage regardless of position, because the capillary bore is of such a diameter that, for the viscosity of the silicone employed, there=wil1 be no flow.

Thesemi-conductor or Thermistor 2S, in and of itself, does not have a variation of resistance with temperature such that it will compensate for the conductivity change in a saline, iluid with temperature. Referring to Fig. 4 the curve A shows the variation of resistance with temperature of the temperature sensitive Thermistor used herein. This curve corresponds to a resistance whose variation with-temperature follows the expression 4 R=RNB T Te wherein R=resistance at any temperature; Ro=6300 ohms at temperature To;

:3450180: T=temperature in degrees Kelvin; and

lb-298.2 K.=25 C.

This characteristic must be modied so that the variation in resistance of the element is essentially the same as the variation in resistance of the liquid whose salinity it is intended to indicate.

By utilizing a network of resistances such es is shown in Fig. 5 the resistance characteristic of theThermistor may be modined so that it is more nearly, or exactly, the variation in resistance with temperature that is required. Experiments show that by making the resistor 3l of 240 ohms, resistor 35 of 330 ohms and resistor f 36 of 6700 ohms, the resistance4 network including the Thermistor 28 which is shown as a variable element will have a total temperature coeiiicient corresponding to that of a salt solution so that in cooperation with the measuring system the net change per degrees C. is negligible. As may be seen from Fig. 4, when the salt solution is relatively cold the Thermistor has a large resistance value, in excess of 5000 ohms. This V resistance is effectively in parallel with resistor 36 so that the total effective resistance is thereby lessened and the network has a marked eifect on the overall response of the Thermistor, limiting the maximumresistance to 6940 ohms. At elevated temperatures, however, it may be seen from curve A of Fig. 4 that the temperature sensitive element has a resistance oi' a few hundred ohms. again is eiiectively in parallel with resistor 36 and even though the added resistance of' resistor 35 is effectively in series, the resistance is so low that resistor 36 has relath ely little eiect. Thus the dynamic range of change in resistance with temperature is lessened so that curve B of Fig. 4 is produced, which curve is essentially the curve for an arbitrarily chosen concentration of salt water.

This concentration, although arbitrary, should be such a concentration as to allow sumcient sensitivity to the system and should therefore be as nearly the highest safe concentration permissible for the application in which the system is employed. The resistors 3l, 35 and 3B are chosen for" a given concentration and once chosen remain fixed, neither changing with temperature nor with current. Minor variations in the assigned values may occur, however, even for an arbitrarily chosen concentration ofvsalt in water, to compensate for minor variations in the cheracteristics of the Thermistor elements themselves.

As thus disclosed, the salinity cell becomes a self-compensating element having, for a lgiven concentration of saline fluid, ay temperature coenicient equivalent to that of the saline fluid under test, and requiring no mechanical or external modifying means other than the i'ixed network disclosed to operate continuously and without attention in a completely accurate and automatic manner.

What is claimed is:

l. An electrode which comprises a thermally and electrically conductive shell,`a semi-conductor having a pair of terminals and a negative temperature co-'emcient of resistance lying within said shell one terminal of which is connected electrically to said shell, a filler comprising neiy comminuted silica granules moistened with a silicone iluid of low viscosity and high thermal conductivity in said shell and coupling said semiconductor thermally to said shell while insulating itelectrically therefrom, and means for coupling a metering circuit to said shell and to theA remaining terminal of said semi-conductor.

2. An electrode which comprises a thermally and electrically conductive shell. said shell bein! sealed at one end and being Aterminated in an open elongated capillnrybore at the other, s semi-conductor having a pair of terminals and a. negative temperature co-emcient of resistance lying within said shell Une terminal of which is connected electrically to said shell, a filler comprising nely comminuted silica. granules moistened with a silicone iluid ot low viscosity and high thermal conductivity in said shell and coupling said semi-conductor thermally to said shell while insulating it electrically therefrom, and means for coupling a metering circuit to said shell and to the remaining terminal of said semiconductor.

6 REFERENCES Cim The following references are of record in they Number Name Date 2,048,047 Austin July 21, 1938 2,370,609 Wilson et al. Feb. 27. 1945 2,450,459 Thomson Oct. 5, 1948 2,456,117 Feller Dec. 14, 1948 2,470,153 Feller May 17, 1949 

